Jaroslav frohlich



Patented Mar. 9, 1926.

UNITED STATES PATENT OFFICE.

JAROSLAV FRbHLICH, OF BASEL, SWITZERLAND, ASSIGNOR TO SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OF BASEL, SWITZERLAND.

DYESTUFFS AND PROCESS OF MAKING SAME.

No Drawing.

To all whom it may concern:

Be it known that I, JAROSLAV FROIVILICH,

a citizen of the Swiss Confederation, and residing at Basel, Switzerland, have invented useful new Dyestuffs and Processes of Making Same, of which the following is a full, clear, and exact specification.

The present invention relates to new vat dyestuffs which are particularly valuable for producing fast tints on the animal fibre. The invention comprises the new dyestuffs, the method of making same, and the material dyed with the new vat dyestuffs,

It has been found that valuable vat dyestuffs are obtained by causing sulfur dichloride to act upon 2:5-diarylidobenzoquinones. This reaction maybe conducted in presence of a diluent and with addition of an agent Wlll(ll binds acids, as for example sodium acetate or magnesium oxide, and a condensing agent, as for example sulphuric acid. The temperature and the proportion which the reacting substances bear to each other may be varied within wide limits.

For obtaining dyestuffs of a darker toneit is in general advantageous to operate at higher temperatures which may rise to the boiling point of the diluent, as for lnstance nitrobenzene.

Particularly suitable for the reaction are 2z5-diarylidobenzoquinones, which are not substituted or are only mono-substituted (in '3- or 6-position) in the quinone nucleus. They react even at ordinary temperature with dyestuff formation, whereas the 3 G-disubstitution-derivatives in most cases require a higher temperature. The 2:5-diarylidobenzoquinones, the manufacture of which is generally known, may be derived from two aromatic amines which may be the same or different and may be mono-substituted at the nitrogen or monoor polysubstituted at any position in the nucleus. As substituents there may be named, among others,halogen alkyl-, alkoxyl- (OCH phenyloxy- (OC H nit-ro-, amino, alkylamino-, aralkylam1no-, phenylamino-, hydroxylor carboxyl-groups,

The dyestuifs thus obtained form dark, yellow to dark blue and black powders and contain sulphur and mostly also halogen. They dissolve in concentrated sulphuric acid to a brown to redvi0let and bluegreen solution. WVith hydrosulphite and caustic soda lye they give light yellow to brown vats Application filed October 21, 1924. Serial No. 745,022.

14.5 parts of 2: 5-dianilidobenzoquinone corresponding wlth the formula:

are stirred into 10 parts of nitrobenzene and mixed gradually at- 5 Cnwith 11.3 parts of sulphur dichloride (SCl Stirring is con-- tinued at this temperature for a long time,

whereupon dilution with alcohol and filtration of the dyestuff which has separated follow. The dyestufl is a bI'OWIIePOWdQI' soluble in concentrated sulphuric acid to a blue-violet solution and yielding a bright vat which dyes wool blackish brown tints.

E mample 2.

290 parts of dry nitrobcnzene and 29 parts of 2 o-dianilidobeuzoquinone are mixed and cooled, while stirring well, to 5 C. and in the course of an hour are mixed with 34 parts of sulphur dichloride. After continued stirring the whole is filtered and the solid product washed and dried. There is thus obtained abrown powder'which dissolves in concentrated sulphuric acid to a violet-blue solution and dyes wool in a hydrosulphite vat full, fast brown tints. If in this example the temperature is raised in the course of a few hours to 5060 C. there is obtained a dyestulf which dissolves in concentrated sulphuric acid to a dirty violet solution and produces on wool a dark brown. If the operation is carried out at still higher temperatures, such as 100110 (3., a dark red dyestuff is obtained which dissolves in concentrated sulphuric acid" to a violet solution and produces a dark redbrown tint on wool. If the reaction is carried out at a still higher temperature, for example at the boiling point of the mixture, there is obtained a dark brown dyestuff.

which dissolves in strong sulphuric acid to a reddish-blue solution and dyes wool in a hydrosulphite vat" fast grey to blackish shades. If the condensation is carried out in concentrated sulphuric acid at ordinary temperature a dyestufl is obtained which dyes'wool olive tinged brown shades;

Example 3.

72 parts of 2 5-dianilidobenzoquinone' are suspended in 1,4 10 parts of nitrobenzene .with addition of 82 parts of calcined sodium acetate. The suspension is mixed gradually at 5 C. with 80 parts of sulphur dichloride and thoroughly stirred for a long time. By filtration and washing with alcohol there is obtained a brown powder which dissolves in concentrated sulphuric acid to a reddishviolet solution and dyes wool in a hydrosulphite vat yellow-olive. By substituting magnesia for the acetate and heating the mixture gradually to 100110 C. there is obtained a dark red powder which dissolves in concentrated sulphuric acid to a violet solution and dyes wool dark red-brown tints. If the temperature is carried to the boiling point of the suspension agent there is obtained in the presenceof magnesia a blue powdehwhich dissolves in concentrated sulphuric acid to a dirty blue solution and dyes wool blue-grey in the vat.

E mample 4.

81 parts of 2:5-dianilido-6-chloro-1:4- benzoquinone corresponding with the formula i 0 II are suspended in 1.000 parts of nitrobenzene and mixed at 5 C. with 12 parts of sulphur dichloride. The whole is stirred for a long time at 5-8 C. Filtration, washing and drying follow as usual; The new dyestufi' is a bright brown powder. soluble in strong concentrated sulphuric acid to a red-violet solution and dyeing wool in the vat yellowbrown.

By increasing the proportion of sulphur dichloride the tint of the dyestufi' is shifted towards red. For example, in the above mixture the use of 26 parts of sulphur dichloride produces a dyestuff which is a reddish-brown powder soluble in concentrated sulphuric acid to a somewhat bluer solution than that of the preceding dyestulf and dye ing wool in the vat orange-brown, Whereas the use of 78 parts of sulphur dichloride. leads to a dyestutf which dyes somewhat redder tints.

If the operation is not conducted in the cold, but the mixture is heated gradually to 100 C. and left for some time at 100120 C. there is produced a dyestufl' which dyes a brown-red; if the temperature is raised to the boiling point a product which dyes blackish-violet-brown is produced.

A- brown-dyeing product which dissolves in sulphuric acid to a violet-blue solution is further obtained by causing sulphur dichloride to react for a short time upon 2 5- dianilido-(S-chloro-l:4-benzoquinone at low temperature and in the absence of a diluent.

Ewamyzle 5.

78 parts of 2:5-dianilido-G-methylbenzoquinone are suspendedin 1,000 parts of ni -t-robenzene and the suspension is mixed at 5 C. with 20 palts of sulphur dichloride. The whole is stirred for some time, whereby a red-brown powder isobtained which dissolves in concentrated sulphuric acid to a reddish-violet solution and dyes wool in the vat full yellow-brown tints. By substituting 78 parts of sulphur dichloride for the 26 parts there is obtained a product which dissolves in sulphuric acid to a dull violet-red solution and yields red-brown tints on wool. By addition of magnesia and raising the temperature to the boiling point of the mixture the dyestuff produced dissolves in sulphuric acid to a dark yellowbrown solution and dyes wool in the vat olive.

' [Trample 6'.

properties of a number of dyestuffs which can be obtained by the present invention Appearance of Colour of the Sulphur halogen Dyeing on wool l Solvent. Tern erature. the d estufi solution in sul- Dmry ldoqumone compounds. p g' phuric acid In the vet.

2:5-para-para-dlchloro- 13 mol. sul- Nitrobenzene Gold l Red blown Red to violet... Yellow-brown.

,dianilido benzoquinone. plur dichlo- :1 e. Do 3 xrol. sulphur ..do 100 C. up to Brown to green- Reddish-blue to Violet-brown to dlch orlde. boiling. ish blue. grey-blue. grey.

- Sulphur halogen Appearance 0019M the Dyeing on wool Diarylldoqumone. Solvent. Temperature. the dyestuflf solution in sulcompounds. powder phmic acid. 111 the vat.

2:5-ortho-ortho-di- 3 mol. sulphur Nitro-benzene... 100 C. up-t-o Brown-black.- Bluee to dull Grey.

c111 orodl-anilidodichloride. boiling. ree rl benzo-qulncne. 1:5-para-para-dl- .....do ..do Coldup toboll- Brown to dark Blu t d ll Violet-grey to toluidldo-benzo-qulm ing. blue. green, gleenishgrey.

one. 2:5-meta-meta-di-tolu- 1 mol. sulphur Cold"... Dark brown. Reddish-violet Olive-brown. ldldo-benro quinone dichloride.

ms-dimeta-xyhdido-benzo- 3 incl. sulphur 100 C Olive B1uish-grey Blue-grey.

quinone. dlchloride. 2:5-di-ortho-anisidido- 3 mol. sulphur, 100 {3. up to Dark blue to Green-blue to -g een.

benzo-quinone. dlchloride. boilingdark green. blue-green. 2:5-dl-orth0-ph n 1d -do do Black to green- Green-blue, Olive t l s benzo-quinone lSh black. green. 2:5-dipara-anisidldonzo- .do do Cold up to boll- Brown-black to 131 m greenish Vlolet-grey quinone, mg. dark blue. blue. o grey-blue. 2:5dipara-phenetldldodo ..do 100 9. up o Blue black to Dull green-blue Blue-gre benzo-quinoue. bolllng. d rk blueto dull blueto green-grey.

gr een. 2:5-diortho-p ny t rdo do Bolllllg Blackish greeu Blu1Sh-g1-ey Bmefieen,

anilido-benzo-qumone. V 2:5 di para phepylether- 3 mol. surphur Nltrobenzene Cold up to boll- Dark red-brown Dirty blue to Brown to greenanilido-benzoqulnou e. dichloride. lng. to black. ive. blue. 2:5-di (a-naphthylam1do)- l-3 moLsulphur do ..d0 Dark blue Dull green to Violet brown, benzoquinone. dichloride. blue-green. blue grey to greenish grey. 2:5 dibenzylamlldobeuzo- 3 mol. sulphur do do Blue Dull blue Blue-grey.

quinone. dichloride. 2:5-di-monomethyl amlidodo .-do.- ..do Blue grey o Dull green Blue grey t benzoquinone. h black. green-grey. 2:5 di crthonitranilidodo ..do 100, o. up to Black-brown to Red-brown to Red brown to benzoquinone. boiling brown black. dull yellowgrey.

green. 2:5-dimeta-nitranilido-ben- 1-3 mol. sulphur do Cold up to boll- Brown to black Brown to blue- Brown to grey.

zoquinone. dichloride. mg. green. 2:5 dipara-oxyanilido-bendo "do .do Red b ow to Blue Yellow brown, zoqulnone. black. olive-brown to grey. 2;5-dianilidobenzoquinonc 3 mol. sulphur Glacial acetic Cold Dark brown.... Dull blue Brown.

dichloride. acid. do Formic acid 0%(1 up to 60 Brown Rgddjllsh -violet Olive to grey.

. o ue. do ochlorouaph- Cold Dark brown. Violet Yellow-brown,

thalene. ,.d 'Orthodichloro- Cold C h 0 c o 1 a t e .....do Dc benzene. brown. do Chlorobenzene Cold ..do 4 dc D do- 1 1e Cold -.do Duty red violet. Olive-brown.

What I claim is 1. As a new process, the manufacture ofvat dyestuifs, which consists in causing sul'-.

As a new process, the manufacture of vat dyestuffs, which consists in causing sulphur dichloride to act upon 2:5-dianilido enzoquinone.

4. As a new process, the manufacture of vat dyestuffs, which consists in causing sulphur dichloride to act upon 2:5-dianilidobenzoquinone in presence of a diluent.

5. As new products, the dyestuffs obtained from 2:5-diarylidobenzoqumones and sulphur dichloride, which form dark yellow to dark blue and black powders, dissolving in concentrated sulphuric acid to brown to redviolet and blue-green solutions and giving with hydrosulphite and caustic soda lye bright yellow to brown vats from which Wool is dyed fast yellow-brown to redbrown, olive-green, green-blue and grey tints.

6. As new products, the dyestuffs obtained from 2 :5-diarylidobenzoquinones and .sulphur dichloride containing sulphur and also chlorine, which form dark yellow to dark blue and black powders, dissolving in concentrated sulphuric acid to brown to redviolet and blue-green solutions and giving with hydrosulphite and caustic soda lye bright yellow to brown vats from which wool isi dyed fast yellow-brown to redbrown, olive-green, green-blue and grey tints.

7. As new products, the dyestud'sobtained from 2:5-dianilidobenzoquinone and sulphur dichloride containing sulphur and also chlorine, which form dark yellow to dark blue and black powders, dissolving in concentrated sulphuric acid to red-violet to blue-violet solutions and. givin with hydrosulphite and caustic soda lye bright yellow to brown vats from which wool is dyed fast yellow-brown to red-brown, violet-brown and vblack-brown tints.

8. Material dyed with the dyestuffs of claim 5; i

9. Material dyed with the dyestuffs of claim 6.

10. Material dyed with the dyestuifs of claim 7.

In witness whereof I have hereunto signed my name this 1st day of October, 1924.

JAROSLAV FRoI-ILroH. 

